CN105624773B - The preparation method and its single crystal grain and solar cell of a kind of micron order copper germanium zinc-tin sulphur single crystal grain - Google Patents
The preparation method and its single crystal grain and solar cell of a kind of micron order copper germanium zinc-tin sulphur single crystal grain Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- PNEOBFGPZMCETM-UHFFFAOYSA-N [S].[Ge].[Sn].[Zn].[Cu] Chemical compound [S].[Ge].[Sn].[Zn].[Cu] PNEOBFGPZMCETM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 229920000084 Gum arabic Polymers 0.000 claims abstract description 25
- 235000010489 acacia gum Nutrition 0.000 claims abstract description 25
- 239000000205 acacia gum Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 78
- 239000011701 zinc Substances 0.000 claims description 16
- 244000215068 Acacia senegal Species 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000013461 design Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 abstract description 2
- 241000978776 Senegalia senegal Species 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 54
- 239000002245 particle Substances 0.000 description 27
- 238000004544 sputter deposition Methods 0.000 description 13
- 239000011135 tin Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- QLMUUIHSNUYEAS-UHFFFAOYSA-N [Ge].[Cu].[Zn] Chemical compound [Ge].[Cu].[Zn] QLMUUIHSNUYEAS-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses the preparation methods and its single crystal grain and solar cell of a kind of micron order copper germanium zinc-tin sulphur single crystal grain, presoma is prepared first, in accordance with the formula reaction raw material of design, by presoma Vacuum Package, melting generation CGZTS single crystal grains under certain temperature；In addition using epoxy resin, gum arabic as macromolecular material, micron order CGZTS single crystal grains is embedded in macromolecular material and prepare single crystal grain film, then prepare various functions layers and form complete battery.The preparation process that preparation and single crystal grain due to single crystal grain absorb tunic is separated, hot environment can be used in single crystal grain preparation process, it is effectively controlled so as to fulfill the component to CGZTS, without regard to absorbed layer preparation condition to substrate, the influence of Window layer, buffer layer etc., this method have apparent advantage in terms of material and energy utilization rate and industrialized production.
Description
Technical field
The present invention relates to photoelectric semiconductor material and device arts, more particularly, to a kind of micron order copper germanium zinc
The preparation method and its single crystal grain and solar cell of tin sulphur single crystal grain.
Background technology
Multi-element compounds CuInGaSe2(CIGS) thin-film solar cells has higher transfer efficiency, is easy to extensive
Production becomes at present the solar cell material of most development potentiality, and CIGS batteries are that opto-electronic conversion is imitated in the world at present
The highest thin-film solar cells of rate, highest transfer efficiency is up to 21.7%.But its component In and Ga are provided on earth
Source lacks, and CIGS hull cell is caused to be difficult to realize terawatt (TW) (109KW) the large-scale application of rank.
Copper-zinc-tin-sulfur (CZTS) base film is considered as most to be hopeful to replace the new of CIGS thin film solar battery obsorbing layer
Type compound semiconductor.At present, the transfer efficiency of CZTS based thin film solar cells has reached 12.6%, and according to theoretical model
It calculates, the limit transfer efficiency of unijunction CZTS base film batteries is up to 30%, and the two differs greatly, even if current most with CIGS
High conversion efficiency 21.7% is compared, and also has larger gap.This illustrates that CZTS base films battery efficiency also has very big promotion
Space.The diffusion length of carrier is less than normal in CZTS base films, causes the charge that material depths generates that cannot effectively be collected, device
Part transfer efficiency is difficult to be promoted, if can effectively be regulated and controled to CZTS films bandwidth, it will guide and enhance electronics
From the depths of film to the diffusion on surface, increase the electric current of device so as to greatly improve charge collection efficiency, improve simultaneously
The open-circuit voltage of device is also very crucial for promoting device efficiency.
At present, polynary coevaporation, pulsed laser deposition, sputtering are mainly concentrated in the preparation of CZTS based solar batteries absorbed layer
The vacuum technologies such as selenizing vulcanization and hot injection, solvent heat, hydro-thermal method, spray pyrolysis etc. are non-after after cure selenizing, electrochemical filming
In vacuum technology, compared with binary and ternary semiconductor, this kind of compound semiconductor of CZTS bases is due to component
Increase, cause it that there is more complicated physical property, therefore preparation and the performance of the high efficiency hull cell of this kind of compound
Optimization becomes more difficult；The Thermodynamically stable region of CZTS phases is very small simultaneously, and various impurity phases, metastable phase and CZTS are mutual
Competition, therefore in CZTS base film preparation process, if being not carried out effective component control, since Partial Elements volatilize,
Lead to nonstoichiometry ratio, easily with there are various binary, ternary dephasign and some metastable phases, finally to CZTS base batteries
Performance brings adverse effect；When preparing solar cell, the performance of the performance ratio hull cell of single crystal battery is more preferable, still,
Traditional Crystal Growth Technique (gas phase transmission technology, fusion technology) is wanted it is difficult to grow and meet solar battery obsorbing layer performance
The large size single crystal asked.
Invention content
The technical problems to be solved by the invention are to overcome existing drawbacks described above, provide a kind of micron order copper germanium zinc
The preparation method of tin sulphur single crystal grain.
Second object of the present invention is to provide the copper germanium zinc-tin sulphur single crystal grain that above-mentioned preparation method obtains.
Third object of the present invention is to provide the solar cell containing above-mentioned copper germanium zinc-tin sulphur single crystal grain.
Fourth object of the present invention is to provide above-mentioned copper germanium zinc-tin sulphur single crystal grain in terms of solar cell is prepared
Using.
The 5th purpose of the present invention is to carry the preparation side of the solar cell containing the copper germanium zinc-tin sulphur single crystal grain
Method.
The purpose of the present invention is what is be achieved by the following technical programs：
A kind of preparation method of micron order copper germanium zinc-tin sulphur single crystal grain, includes the following steps：
S1. by reaction raw materials elemental copper powder/CuS powder, simple substance zinc powder/ZnS powder, simple substance tin powder/SnS powder
End, simple substance sulfur powder and elemental Germanium powder are mixed in a certain ratio, and add in fluxing agent, and ground and mixed is uniformly configured to presoma；
S2. presoma is fitted into quartz reaction container, quartz reaction container is sealed after vacuumizing or being passed through inert gas；
S3. the quartz reaction container after sealing is kept into 48~120h at 600~1000 DEG C, it is fast to quartz reaction container
Prompt drop warms to room temperature, and the sample in quartz reaction container is taken out, up to copper germanium zinc-tin sulphur single crystal grain after washing, drying；
Copper in reaction raw materials described in S1, zinc, germanium, tin, five kinds of elements of sulphur molar ratio be：Cu/ (Zn+Ge+Sn)=0.76
~0.95, Zn/ (Ge+Sn)=1.1~1.2, Ge/Sn=0.3~1, (Cu+Ge+Zn+Sn)/S=0.8~1.2.
The present invention is by metal powder (Cu, Zn, Sn), elemental Germanium powder, simple substance sulfur powder, sulfide (CuS, ZnS, SnS)
Powder is mixed according to designed ratio, and adds in fluxing agent, is fully ground and is mixed and made into presoma, under high temperature fused state
Recrystallization generation CGZTS single crystal grains；Crystal grain is grown under equilibrium state in fused salt, when particle shape and size reach
During to design requirement, fast cooling is carried out to reaction vessel, inhibits the nonequilibrium state growth of crystal in temperature-fall period, so as to control
The pattern of single crystal grain；The size of single crystal grain can be regulated and controled using recrystallization temperature and time, the ingredient of single crystal grain
It can effectively be allocated in a certain range by the molar ratio of each element in presoma；The introducing of Ge elements so that CZTS bases
The bandwidth of absorbed layer can be adjustable in the range of 1.0~1.5eV.
Single crystal grain because with the performance more excellent than thin-film material, having obtained people and widely having paid close attention to, using pattern rule,
The uniform single crystal grain of component prepares solar cell, since each single crystal grain forms a battery unit, can effectively drop
The influence of low absorption layer defects and interface impurity to device performance, the single crystal grain of almost spherical forms mound shape absorbing surface can be effective
The utilization rate of incident light is improved, there is advanced optical characteristics, significantly promotes the transfer efficiency of CZTS base batteries, the prior art
The pattern that single crystal grain is prepared using molten-salt growth method is uncontrollable, and component is uneven, and the time for forming single crystal grain is too long, is unfavorable for
Reaction raw materials and fluxing agent are ground by industrial production, the invention, by vacuum sealing, high-temperature fusion, are tied again
Crystalline substance obtains morphology controllable, the controllable single crystal grain of component.
In fact, the single crystal grain that preparation meets solar battery obsorbing layer is extremely difficult, to combine practical to be prepared
The element composition of single crystal grain, the growth technique of raw material proportioning and monocrystalline, can just finally obtain qualified single crystal grain, only
It is that control element forms, raw material proportioning is not likely to that single crystal grain is caused to prepare failure in suitable range；The present invention with
Molten-salt growth method is prototype, uniformly sealing is vacuumized by the way that reaction raw materials and fluxing agent are ground according to a certain percentage, by it one
React certain time at fixed temperature, when reaction generates ideal size pattern, by fast cooling inhibit crystal into
One step growth, timely cooling and suitable temperature can effectively prepare the micron single crystal grain of ideal dimensions size.
Preferably, the mixing molar ratio of the fluxing agent and reaction raw materials is 1~10：1.
Preferably, it is 10~10 that the vacuum degree in rear quartz reaction container is vacuumized described in S22Pa。
Preferably, fluxing agent described in S1 is one or more in CsCl, KCl, KI.
The present invention provides the micron order copper germanium zinc-tin sulphur single crystal grains that a kind of above method obtains.
The present invention also provides application of the copper germanium zinc-tin sulphur single crystal grain in terms of solar cell is prepared.
The present invention also provides the solar cells containing the copper germanium zinc-tin sulphur single crystal grain.
The preparation method of the solar cell, includes the following steps：
S1. one layer of gum arabic film is prepared on substrate using czochralski method；
S2. after acacia gum layer curing, adhesive layer is coated on acacia gum layer, treats adhesive layer semi-solid preparation
When, the copper germanium zinc-tin sulphur single crystal grain that grain size is 40~70 μm is embedded in adhesive layer；The copper germanium zinc-tin sulphur single crystal grain
Volume ratio with adhesive layer is 1：1.5~2；
S3. cured, grinding, cleaning, etching obtain copper germanium zinc-tin sulphur list after exposing copper germanium zinc-tin sulphur single crystal grain surface
Brilliant particle film；
S4. back electrode layer, CdS buffer layers, Window layer i-ZnO and the transparent electrode layer AZO of single crystal grain film are made, is steamed
Plated electrode is encapsulated to get no substrate copper germanium zinc-tin sulphur single crystal grain flexible solar battery.
Adhesive described in S2 is selected from epoxy resin, polyurethane adhesive, silicon rubber.
Specifically, S4 is specially following operates：(1) cured, grinding, is carved at cleaning (being cleaned using HCl and deionized water)
Erosion (etch period is 1~3min) obtains copper germanium zinc-tin sulphur single crystal grain film after exposing single crystal grain surface；(2) it is exposing
The molybdenum film of 1~2 μm of the surface sputtering sedimentation of single crystal grain is as back electrode layer；(3) sample is taken out, detaches single crystal grain film
And dry, single crystal grain film is laid in hard substrates, the surface for being coated with molybdenum film downward, etches away single crystal grain surface
Remaining gum arabic and adhesive (etch period is 5~15min)；(4) CdS is sequentially prepared on single crystal grain film to delay
Layer, Window layer i-ZnO and transparent electrode layer AZO, electrode evaporation are rushed, is encapsulated soft to get no substrate copper germanium zinc-tin sulphur single crystal grain
Property solar cell.
The preparation of existing thin-film solar cells and film be while, the preparation of such film absorption layer can then influence too
The performance of positive energy battery, the present invention are used as the main component of film absorption layer by the single crystal grain that molten-salt growth method is prepared, with
Epoxy resin prepares the flexible unitary particle film absorbed layer of function admirable as adhesive layer；Due to single crystal grain
The defects of using, one battery unit of each single crystal grain formation, reducing film absorption layer and interface impurity are to device performance
It influences, which can be used for follow-up preparation thin-film solar cells.
Inventors discovered through research that in fact, it is difficult system just with single crystal grain, gum arabic and epoxy resin
It is standby go out suitable single crystal grain film, it is necessary to thickness, single crystal grain and the epoxy of stringent control gum arabic and epoxy resin
The proportioning of resin can just successfully obtain single crystal grain.
Preferably, the thickness of the gum arabic film described in S1 is 10~20 μm.
Preferably, adhesive layer coating thickness described in S2 is 80~100 μm.
Preferably, the grinding described in S3 refers to grind adhesive layer, and the thickness for grinding removal is 50~80 μm.
Preferably, the thickness of the CdS buffer layers is 40~60nm；The Window layer i-ZnO's and transparent electrode layer AZO
Thickness is respectively 100~400nm and 0.4~1 μm.
Compared with prior art, the invention has the advantages that：
The present invention provides the preparation methods and its single crystal grain and the sun of a kind of micron order copper germanium zinc-tin sulphur single crystal grain
Energy battery, i.e., according to the formula reaction raw material of design, then addition fluxing agent, which is fully ground, is mixed with presoma, by before
It drives body powder under vacuum to be encapsulated in quartz reaction container, quartz reaction container is put into Muffle furnace, melted at a temperature of setting
Melt recrystallization generation CGZTS single crystal grains；The size of prepared single crystal grain can be adjusted using the temperature and time of recrystallization
Control, the ingredient of particle can effectively be allocated in a certain range by the molar ratio of each element in presoma, single crystal grain
Bandwidth can be controlled by regulating and controlling Ge contents, and preparation-obtained single crystal grain ingredient is uniform, size is controllable, and performance is excellent
In the single crystal grain that conventional method is prepared；In addition by big point of the CGZTS single crystal grains for the micron level being prepared insertion
The single crystal grain film of individual layer is prepared in sub- material, removes the bonding on two sides by mechanical lapping and plasma etching again later
Agent leaks out single crystal grain, prepares the functional layers such as buffer layer, Window layer, electrode so as to form complete battery structure.Due to monocrystalline
The preparation process that preparation, screening, cleaning, passivating process and the single crystal grain of particle absorb tunic is separated, in single crystal grain
It prepares and harsh hot environment can be used in optimization process, effectively controlled so as to fulfill component, the band gap to CGZTS
System, without regard to influence of the absorbed layer preparation condition to substrate, Window layer, buffer layer etc., this method is in material and energy profit
There is apparent advantage with rate and industrialized production aspect.
Description of the drawings
Fig. 1 is that the EDAX of 1 sample particle of embodiment schemes.
Fig. 2 is the surface topography of 1 sample particle of embodiment.
Fig. 3 is the surface topography of 4 sample particle of comparative example.
Fig. 4 is the surface topography of 5 sample particle of comparative example.
The preparation process of Fig. 5 solar film batteries of the present invention；Wherein, Fig. 5 (1) is made on common glass substrate
Standby gum arabic；Fig. 5 (2) is that epoxy resin is coated on gum arabic, by CGZTS monocrystalline after epoxy resin semi-solid preparation
In particle insertion adhesive layer；Fig. 5 (3) is to grind away one layer of epoxy resin to make CGZTS single crystal grain surface exposures；Fig. 5 (4) is
With sputtering method Mo back electrode layers are prepared on the surface for exposing CGZTS single crystal grains；Fig. 5 (5) is to impregnate to divide in deionized water
From taking film off after substrate and acacia gum layer and drying, be coated with Mo films one is placed face down in support substrate.
Fig. 6 is the preparation process of solar film battery of the present invention, wherein, Fig. 6 (1) is with plasma etching
The gum arabic and epoxy resin of grain remained on surface make the spherical surface of film exposing CGZTS single crystal grains；Fig. 6 (2) is to use
CBD methods prepare CdS buffer layers on the surface of CGZTS single crystal grains；Fig. 6 (3) is to prepare i- on CdS buffer layers with sputtering method
ZnO Window layers；Fig. 6 (4) is that AZO transparent electrode layers are prepared in i-ZnO Window layers with sputtering method；Fig. 6 (5) is electrode evaporation,
Encapsulation is prepared and is completed without substrate CGZTS single crystal grain flexible solar batteries；
Reference sign：11- single crystal grains；12-CdS buffer layers；13-i-ZnO Window layers；14-AZO transparent electrodes
Layer；15-Mo films；21- epoxy resin；22- gum arabics；31；32- substrates (such as glass substrate)；41- encapsulating materials EVA.
Specific embodiment
The content further illustrated the present invention with reference to the accompanying drawings of the specification with specific embodiment, but should not be construed as to this
The limitation of invention.Without departing from the spirit and substance of the case in the present invention, the method for the present invention, step or condition are made simple
Modifications or substitutions all belong to the scope of the present invention；Unless otherwise specified, technological means used in embodiment is art technology
Conventional means known to personnel.
Embodiment 1
Weigh reaction raw materials 18mmol CuS, 12mmol ZnS, 5mmol Ge, 5mmol SnS, 15mmol S and fluxing agent
120mmol CsCl are fully ground after mixing, are uniformly mixed it；Mixed sample is fitted into quartzy bottle, utilizes vacuum
Pump assembly, which vacuumizes, reaches 10~102Pa (can also blanketing with inert gas), so as to exclude the influence that air reacts fused salt,
With oxyhydrogen flame by quartzy bottle closure；The quartzy bottle that mixing sample is housed after sealing is placed in common heating furnace and is heated to from room temperature
Then 800 DEG C of holding 72h cool to 600 DEG C and take out quartzy bottles and fast cooling is to room temperature (into the water)；Finally by quartzy bottle
In sample take out, ultrasound washing repeatedly remove fluxing agent CsCl, sample is placed in the dry 2h of 80 DEG C of drying box later, obtains table
Micron-scale CGZTS single crystal grain of the face with crystal gloss, about 65 microns.
The EDAX results of 1 sample of embodiment are shown as CGZTS particles, granule-morphology rule, carrier concentration for 1.29 ×
1016/cm-3, mobility 36.20cm2·V-1·s-1, resistivity is 13.38 Ω cm, and band gap width is about 1.34eV.
Embodiment 2
Weigh reaction raw materials 22mmol Cu, 15mmol Zn, 5mmol Ge, 8mmol Sn, 50mmol S and fluxing agent
120mmol KI are fully ground after mixing, are uniformly mixed it；Mixed sample is fitted into quartzy bottle, utilizes vacuum pump
Unit, which vacuumizes, reaches 10~102Pa (can also blanketing with inert gas) so as to exclude the influence that air reacts fused salt, is used
Oxyhydrogen flame is by quartzy bottle closure；The quartzy bottle that mixing sample is housed after sealing is placed in common heating furnace and is heated to from room temperature
Then 850 DEG C of holding 66h cool to 600 DEG C and take out quartzy bottles and fast cooling is to room temperature (into the water)；Finally by quartzy bottle
In sample take out, ultrasound washing repeatedly remove fluxing agent KI, sample is placed in the dry 2h of 80 DEG C of drying box later, obtains surface
Micron-scale CGZTS single crystal grains with crystal gloss, about 58 microns.
The EDAX results of 1 sample of embodiment are shown as CGZTS particles, granule-morphology rule, carrier concentration for 1.22 ×
1016/cm-3, mobility 29.80cm2·V-1·s-1, resistivity is 17.19 Ω cm, and band gap width is about 1.40eV.
Embodiment 3
Solar cell is prepared using single crystal grain described in embodiment 1, is included the following steps：
1. prepare the gum arabic film that a layer thickness is 15 μm on substrate using czochralski method；
2. after acacia gum layer curing, it is 80 μm of epoxy resin layers that a layer thickness is coated on acacia gum layer,
Then the CGZTS single crystal grain 20g that grain size is about 65 μm are weighed, are uniformly embedded into single crystal grain when epoxy resin layer semi-solid preparation
In epoxy resin layer；The volume ratio of the single crystal grain and epoxy resin is 1：1.7；
3. after epoxy resin cure, the epoxy resin on 55 μm of surface layer is ground away using grinder, exposes CGZTS monocrystalline
Grain surface；
4. cleaning up the surface for exposing CGZTS single crystal grains using HCl and deionized water, dry.
5. film is etched 2min in plasma etching room, film is then sent into sputtering chamber, is exposing monocrystalline
The molybdenum film of 2 μm of the surface sputtering sedimentation of particle is as back electrode layer；
6. taking out sample, impregnate in deionized water and single crystal grain film is detached and dried from substrate, monocrystalline
Grain film is laid in hard substrates, and the surface for being coated with molybdenum film downward, etches away the Arabic tree of single crystal grain remained on surface
Glue and epoxy resin；
7. preparing the CdS buffer layers of 50nm on CGZTS single crystal grains surface using CBD methods, then CdS bufferings will be prepared for
The film of layer is sent into sputtering chamber, the i-ZnO layers and 1 μm of AZO films that prepared by successively sputtering is about 200nm on CdS buffer layers；
8. taking down support substrate, electrode evaporation encapsulates to be formed completely without substrate CGZTS single crystal grains using EVA material
Flexible solar battery.
The film preparation solar cell for the Mo/CGZTS/CdS/i-ZnO/AZO structures that the present embodiment is prepared, is opened
Road voltage Voc=446mV, I=22mA, FF=47%, the conversion ratio of battery is 6.4%.
Embodiment 4
Solar cell is prepared using single crystal grain described in embodiment 2, is included the following steps：
1. prepare the gum arabic film that a layer thickness is 15 μm on substrate using czochralski method；
2. after acacia gum layer curing, it is 85 μm of epoxy resin layers that a layer thickness is coated on acacia gum layer,
Then the CGZTS single crystal grain 20g that grain size is about 58 μm are weighed, are uniformly embedded into single crystal grain when epoxy resin layer semi-solid preparation
In epoxy resin layer；The volume ratio of the single crystal grain and epoxy resin is 1：1.8；
3. after epoxy resin cure, the epoxy resin on 62 μm of surface layer is ground away using grinder, exposes CGZTS monocrystalline
Grain surface；
4. cleaning up the surface for exposing CGZTS single crystal grains using HCl and deionized water, dry.
5. film is etched 2min in plasma etching room, film is then sent into sputtering chamber, is exposing monocrystalline
The molybdenum film of 2 μm of the surface sputtering sedimentation of particle is as back electrode layer；
6. taking out sample, impregnate in deionized water and single crystal grain film is detached and dried from substrate, monocrystalline
Grain film is laid in hard substrates, and the surface for being coated with molybdenum film downward, etches away the Arabic tree of single crystal grain remained on surface
Glue and epoxy resin；
7. preparing the CdS buffer layers of 50nm on CGZTS single crystal grains surface using CBD methods, then CdS bufferings will be prepared for
The film of layer is sent into sputtering chamber, the i-ZnO layers and 1 μm of AZO films that prepared by successively sputtering is about 200nm on CdS buffer layers；
8. taking down support substrate, electrode evaporation encapsulates to be formed completely without substrate CGZTS single crystal grains using EVA material
Flexible solar battery.
The film preparation solar cell for the Mo/CGZTS/CdS/i-ZnO/AZO structures that the present embodiment is prepared, is opened
Road voltage Voc=436mV, I=21mA, FF=49%, the conversion ratio of battery is 6.7%.
Comparative example 1
Experimental method with embodiment 1, it is unique unlike, control the molar ratio Cu/ (Zn+ of five kinds of elements in reaction raw materials
Ge+Sn)=1.5, the property for finally obtaining particle is detected, the results showed that：Under conditions of copper-rich, the condition of copper-rich is held
The easily other copper-based compounds of generation, particle resistivity is relatively low, is not suitable for the absorbed layer as solar cell..
Comparative example 2
Experimental method with embodiment 1, it is unique unlike, control the molar ratio Zn/ (Ge+ of five kinds of elements in reaction raw materials
Sn)=2, the property for finally obtaining particle is detected, the results showed that：Under conditions of zinc-rich, particle surface easily generates
Zinc-rich phase forms boundary defect when preparing hetero-junction solar cell, reduces the efficiency of battery.
Comparative example 3
Experimental method with embodiment 2, it is unique unlike, control the molar ratio Zn/ (Ge+ of five kinds of elements in reaction raw materials
Sn)=1.5, Ge/Sn=1.5, the property for finally obtaining particle is detected, the results showed that：In particle containing zinc-rich phase and
Other compounds of germanium are not pure CGZTS single crystal grains, it is impossible to be answered as solar battery obsorbing layer material
With.
Comparative example 4
Experimental method with embodiment 1, it is unique unlike, presoma is directly placed into quartzy bottle and reacted without grinding,
The property of CGZTS particles finally obtained is detected, the results showed that：Sample particle size is smaller, and grain shape is irregular,
It is difficult to be applied as solar battery obsorbing layer material.
Comparative example 5
Experimental method uniquely the difference is that, does not add fluxing agent, to obtained sample particle with embodiment 1 in raw material
Property be detected, the results showed that：Prepared grain shape differs, and particle clusters phenomenon is apparent, it is difficult to as solar energy
Battery obsorbing layer material is applied.
Comparative example 6
Experimental method uniquely the difference is that, does not vacuumize quartzy bottle or filling with inert gas is protected with embodiment 1
Shield, the results showed that：Quartzy bottle bursts in sample is prepared, and can not prepare CGZTS single crystal grains.
Comparative example 7
Experimental method is unique the difference is that the thickness of gum arabic is 60 μm with embodiment 3, the results showed that：It is cleaning
Has there is the phenomenon that largely coming off in single crystal grain when gum arabic, leads to not prepare with reference to stable monocrystalline
Grain film, further, can not prepare no substrate flexible unitary particle film solar cell.
Comparative example 8
Experimental method is unique the difference is that 20 μm of the thickness of epoxy resin with embodiment 3, the results showed that：Single crystal grain without
Method is completely fixed in adhesive layer, is easily come off with single crystal grain in process of lapping cleaning, is led to not prepare combination
Stable flexible unitary particle film further, can not prepare no substrate flexible unitary particle film solar cell.
Claims (9)
1. a kind of preparation method of micron order copper germanium zinc-tin sulphur single crystal grain, which is characterized in that include the following steps：
S1. by reaction raw materials elemental copper powder/CuS powder, simple substance zinc powder/ZnS powder, simple substance tin powder/SnS powder, list
Matter sulfur powder and elemental Germanium powder are mixed in a certain ratio, and add in fluxing agent, and ground and mixed is uniformly configured to presoma；
S2. presoma is fitted into quartz reaction container, quartz reaction container is sealed after vacuumizing or being passed through inert gas；
S3. the quartz reaction container after sealing is kept into 48~120h at 600~1000 DEG C, to the fast prompt drop of quartz reaction container
It warms to room temperature, the sample in quartz reaction container is taken out, up to copper germanium zinc-tin sulphur single crystal grain after washing, drying；
Copper in reaction raw materials described in S1, zinc, germanium, tin, five kinds of elements of sulphur molar ratio be：Cu/ (Zn+Ge+Sn)=0.76~
0.95, Zn/ (Ge+Sn)=1.1~1.2, Ge/Sn=0.3~1, (Cu+Ge+Zn+Sn)/S=0.8~1.2.
2. preparation method according to claim 1, which is characterized in that the mixing molar ratio of the fluxing agent and reaction raw materials
It is 1~10：1.
3. the micron order copper germanium zinc-tin sulphur single crystal grain that any one of claim 1 to 2 preparation method obtains.
4. application of the copper germanium zinc-tin sulphur single crystal grain in terms of solar cell is prepared described in claim 3.
5. the solar cell containing copper germanium zinc-tin sulphur single crystal grain described in claim 3.
6. the preparation method of solar cell described in claim 5, which is characterized in that include the following steps：
S1. one layer of gum arabic film is prepared on substrate using czochralski method；
S2. after acacia gum layer curing, adhesive layer is coated on acacia gum layer, when adhesive layer semi-solid preparation,
The copper germanium zinc-tin sulphur single crystal grain that grain size is 40~70 μm is embedded in adhesive layer；The copper germanium zinc-tin sulphur single crystal grain and glue
The volume ratio of adhensive layer is 1：1.5~2；
S3. cured, grinding, cleaning, etching obtain copper germanium zinc-tin sulphur monocrystalline after exposing copper germanium zinc-tin sulphur single crystal grain surface
Grain film；
S4. back electrode layer, CdS buffer layers, Window layer i-ZnO and the transparent electrode layer AZO of single crystal grain film, vapor deposition electricity are made
Pole is encapsulated to get no substrate copper germanium zinc-tin sulphur single crystal grain flexible solar battery；
Adhesive described in S2 is selected from epoxy resin, polyurethane adhesive, silicon rubber.
7. the preparation method of solar cell according to claim 6, which is characterized in that the gum arabic film described in S1
Thickness be 10~20 μm.
8. the preparation method of solar cell according to claim 6, which is characterized in that adhesive layer coating thickness described in S2
It is 80~100 μm.
9. the preparation method of solar cell according to claim 6, which is characterized in that the grinding described in S3 refers to grind glue
Adhensive layer, the thickness for grinding removal are 50~80 μm.
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